2-mercapto, alkanol pyridine-nu-oxides



Z-MERCAPTO, ALKANOL PYRID INE-N-OXIDES Francis E. Cislak, Indianapolis, Ind., assignor to Reilly nited States Patent 10 Tar & Chemical Corporation, Indianapolis, Ind., a corporation of Indiana No Drawing. Application July 23, 1956,

Serial No. 599,324

7 Claims. c1. zen-294.8

R R (stin -040E134 where x and y are 0, 1, or 2 and they may be alike or different, A and A are either hydrogenor hydroxyl, R

liter flask equipped with a stirrer. .The solution is heated to a temperature of about 70 C. and while stirring the solution there is added. to it a solution of 50 grams of sodium hydrosulfide in '200 cc. of water. After all of the sodium hydrosulfide solution has been added, the temperature of the reaction mixture is raised to about 85 C. and the stirring and heating continued for about one-half to one hour. Then, there is added about 5 to grams of decolorizing carbon, and the mixture is filtered hot. The filtrate is cooled to about -25 C. and made acid (pH 1.7) with hydrochloric acid. The 2-mercapto-4-(1- propan-3-ol)pyridine-N-oxide may be recovered in any is hydrogen or lower alkyl, and R is hydrogen, lower alkyl, hydroxy-lower alkyl, benzyl, or benzhydryl.

In general the compounds of my invention may be prepared by the reaction of the corresponding 2-halogeno compound with an alkali metal hydrosulfide. The equation below portrays the preparation. of 2-mercapto-4-(1- prop an-3 -01) pyridine-N-oxide c nnomonion omcnzonzon Q NaSH +NaO1 o1 -sn N N/ J t o 0 be understood, however, that these examples are given by way of illustration only and that the invention is not to be limited by the details set forth therein.

EXAMPLE 1 2-mercapt0-4-(1 -pr0pan-3-ol) pyridine-N-oxide (iIHtC H2 OHzO H A solution of 90 grams of 2-chloro-4-(l-propan-3-ol)- 7 EXAMPLE 2 2-mercapt0-6- (1-propan-3-ol)pyridine-N-oxide HO CHiCHnCHP The procedure of Example 1 is followed with the exception that 2-chloro-6-(l-propan-3-ol)pyridine-N-oxide is used in place of the 2-chloro- 4-(,l-propan-3-ol)pyridine- N-oxide.

EXAMPLE 3 2-mrcapl o 6-methdnolpyridine-N-oxide The procedure of Example 1 is followed with the exception that 2-chloro6-methanolpyridine-N-oxide is used in place of the 2-chloro-4-(l-propan-3-ol) pyridine-N- oxide.

' EXAMPLE 4 2-mercapto-3-ethyl-6- I -propan-3-0l pyridine-N-oxide HO CHaCHsCH N SH The procedure of Example 1 is repeatedwith the expyridine-N-oxide in 500 cc. of water is placed in a twoception that 2-chloro-3-ethyl-6-(1-propan-3-ol)pyridine- 3 N-oxide is used in place of the 2-chloro-4-(l-propan 3- ol)pyridine-N-oxide.

EXAMPLE 5 2-mercapt0-6- (1-ethan-2-ol)pyridine-N-oxide Hoomon. sn

The procedure of Example '1 is repeated with the exception that 2-chloro-4-(.1-propan-3-ol) 6-( 1-ethan-2-ol) pyridine-Nmxide is used in place of the 2-chloro-4- (1- propan-3=ol)pyridine-Nwxide.

EXAMPLE 7 2 mercapto-fi-ethyl-6- 1 -ethzm-2-0l pyridine-N -oxid e -CzH5 HO CHaCHr N SH The procedure of Example I is followed with the exception that 2-chloro-3-ethyl-6-(1-cthan-2-o1)pyridine-N- oxide is used in place of the 2-chloro-4-(1-propan-3-ol)- pyridine-N-oxide.

EXAMPLE 8 2-mercapt0-6-(I-ethan-I-ol)pyridine-N-oxide on? sn The procedure of Example 1:isifollowedwith the exception that 2-chloro-6-(l-ethan-1-ol)pyridine-N-oxide is used in place of the 2-chloro-4-(l-propan-3-ol)pyridine- N-oxide.

The Z-mercaptoalkanolpyridine-N-oxides of my invention are alcohols and as such have the chemical properties associated with alcohols and are capable of entering into the same type of reactions as other primary alcohols. Of the many possible reactions ofthe alcohol group of my Z-mercaptoalkanolpyridine-N-oxides, .the one of most commercial significanceis that of .esterification.

The 2-rnercaptoalkanolpyridine N-oxides are also mercaptans and as such have the chemical properties associated with mercaptans and are capable of forming salts by reaction :with \alkali metal carbonates and hydroxides and with alkaline earth metal carbonates and hydroxides. They also can form other metallic salts, such, for example, as those of zinc,.rnercury, iron, etc.

The Z-mercaptoalkanolpyridine-N-oxidcs can also form quaternary ammonium salts and amine-addition salts.

The compounds of my invention are useful as antibacterial and antifungal agents. They may be useful as fungicides and .as chemotherapeutic agents.

My 2-mercaptoalkanolpyi-idine N-oxides mayalso be used forthe preparation of alkyd type polyester resins having a number of 2-mercaptopyridine-N-oxide groups in the resin molecule. Thus, the resin formed from glycerol, phthalic anhydride, and 2-mercapto-4-(1-propan-3-ol)pyridine-N-oxide may be represented as having the structure:

The presenceof the Z-mercaptopyridine-N-oxide group in the resin molecule imparts increased resistance to mildew and other fungus attack. This resistance to fungus attack makes these resins particularly useful in the formulation of outside white paints. Similar resins made from terephthalic acid are useful in making mildew resistant fibers of the Dacron type.

The 2-mercaptoalkanolpyridine-N-oxides may be reduced to the corresponding Z-mercaptoalkanolpyridines which are useful pickling inhibitors.

I claim as my invention:

1. 2-mercaptoalkanolpyridine N-oxides having the general formula:

where x and y are integers selected from the group consisting of 0, 1, and 2, A and A are one of the group consisting of hydrogen and hydroxyl, R is one of the group consisting of hydrogen and lower alkyl, and R is one of the .group consisting of lower alkyl, hydrogen, hydroxy-lower alkyl, and benzyl.

2. 2-mercapto-4-('1-p1'0pan-3-ol)pyridine-N-oxide.

3. 2-mercapto-6-(1-propan-3-ol)pyridine-N-oxide.

4. 2-mercapto-3-ethyl-6-(1-propan-3 ol)pyridine N- oxide.

5. 2-mercapto-6-methanolpyridine-N-oxide.

6. 2-mercapto-3ethyl-6-(1 ethan 2 ol)pyridine N- 'oxide.

7. The process of preparing the compounds of claim 1 which comprises reacting a 2-chloro-alkanolpyridine- .N.-oxide of the general formula:

where xgand y are integers selected from the group consisting of O, 1, and 2,.A and A are one of the group consisting of hydrogen and hydroxyl, R is one of the group consisting of hydrogen and lower alkyl, and R is one of the group consisting of lower alkyl, hydrogen, hydroxylower alkyl, and benzyl Witha member of the group consisting of alkali metal hydrosulfides, alkali metal sulfides, and alkaline earth metal hydrosulfides, and recovering the 2rmercapto-alkanolpyridine-N-oxide.

No references cited. 

1. 2-MERCAPTOALKANOLPYRIDINE-N-OXIDES HAVING THE GENERAL FORMULA: 